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FORMULATION LOGICS IN SPINEL CASTABLES

by Thomas A. Bier, Christopher Parr, Catherine Revais presented at the XXVI ALAFAR Congress, San Juan de Puerto Rico; 1997.

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Abstract
Spinel castables can be achieved either by adding a pre-formed spinel aggregate or by the reaction of MgO with Al2O3 to form in situ spinels. Besides the problems of high temperature behavior, the formulation of such castables presents also a challenge in terms of controlling workability and set behavior. This paper compares different systems suited to achieve a spinel castable and gives results mostly on controlling and understanding the rheology of such systems. Examples for laboratory systems and their admixtures are given.

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Introduction

Until recently ladle linings have been the domain of bricks because the severe conditions in this environment did not allow the use of monolithics. Developments over the last 10 years in the Americas, in Europe and Asia (Japan) resulted in castables which perform very well in different areas of steel ladles, allowing a clean steel technology1. These monolithics together with developed installation techniques, are nowadays produced and used on an industrial level. In order to obtain good performance, especially when in contact with liquid iron and slag, castables are used which contain spinel. These minerals are a family of similar crystallographic structures (lattices) which are being made of different oxides e.g. Al2O3 -MgO; Cr2O3-MgO, FeO-Fe2O3. For spinel castables there is always the Al2O3-MgO type used which might vary only by the Al2O3/MgO ratio. Formulation logic with respect to spinel In order to obtain a spinel castable, preformed spinel can be added as an aggregate2. This logic has the advantage that the spinel has been synthetized before and is present at lower (~1200C) usage temperatures. No problems with volume expansion should be encountered. The second approach is the in-situ formed spinel3. In this case alumina and magnesia are added separately to the castable and spinel is being formed at fairly high temperatures of about 1400-1500C. The castable is difficult to formulate, because MgO is very reactive (slaking) and spinel formation exhibits a volume increase which has to be controlled4.

This logic is rewarded, however, by a very finely dispersed spinel in the matrix which leads to a high penetration resistance by trapping and blocking of slag. The sketch in Figure 1 shows the major differences between spinel and spinel forming castables.
Two approaches to obtain a "Spinel" castables Spinel Castables "preformed" Castables based on Aluminous raw materials with an addition (20-35%) of prereacted spinel aggregate and powder. "in situ" Castables based on Aluminous aggregate with an addition of Magnesia. The spinel phase is formed "in situ" by the action of heat during the operation of the ladle. Type : Alumina - MgO Al2O3 + MgO ULCC / LCC Type

Type : Alumina - Spinel

Al2O3 + Al2O3.MgO MCC Type

Within each generic there exists many formulations, all designed to meet the demands of differing ladle environments.

Figure 1. Comparison of preformed and in-situ formation of spinel.

Formulation logic with respect to CAC's Calcium aluminates cements (CAC) are the preferred binders for the elaboration of spinel castables. As for the spinel formation two different logics exist: one approach via a 70% Al2O3 cement or by using a CAC with 80% cement. Figure 2 shows these two logics in terms of a basic composition for a spinel and a spinel forming castable.

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Raw Material (%) 100 80 60 40 20 0

Experimental approach

Raw materials and formulations Two base formulations of the preformed spinel type and the in-situ spinel forming have been employed using a 70% Calcium Aluminate Cement. 80% Al2O3 Cements have been tested in the pre-formed spinel formulation. Table I compares the three mix designs. The particle size distributions are given as a loglog plot in Figure 3. The target distributions were calculated according to the Andreasen model with a distribution modulus of 0,22. This would provide a compromise between optimum dense particle packing and ideal placing characteristics. We see quite clearly that the presence of silica fume changes the particle size distribution significantly through the addition of ultrafines. Using ultra fine alumina alone it is not possible to exactly match the ideal curve. Table II gives the origin of the raw materials used.
Table I. Comparison of the formulations used System 1 Tabular Alumina (mesh) 1/4 - 8 8 - 14 14 - 28 - 48 - 100 - 325 Spinel (mm) 0,5 - 1 0,5 - 0 0,045 Silica Fume Reactive Alumina Magnesia 70% CAC 80% CAC Water 33 16 6 5 9 4 10 7 10 5 System 2 33 16 6 5 9 4 10 11 6 5 System 4 20 25 10 12 10 5 2 8 5 3 5,5

Alumina

Spinel Magnesia

Silica Fume

Reactive Alumina Cement

System 1 : System 2 : System 3 : System 4 :

Preformed with 80% Al2O3 CAC Preformed with 70% Al2O3 CAC In situ with 80% Al2O3 CAC In situ with 70% Al2O3 CAC

Figure 2. Comparison of formulation logic for 70% Al2O3 and 80% Al2O3 Calcium Aluminate Cement.

We end up with four different ways to design a spinel castable using between 4 and 6 major raw materials. In this sense a preformed spinel with a 80% CAC (System 1) is probably the easiest way to achieve a good product. But it might be more expensive and less flexible than a formulation using in-situ spinel forming with a 70% CAC. The flexibility of the more complicated system 4 bears a good potential of better performance in the ladle since a finer spinel distribution, in the final, fired monolithic can be achieved.

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Additives

System 4 System 3 System 2 System 1

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100 System 2 System 4

To express the flow value in percent we calculate : FV [%] = cake diameter - initial diameter . 100 initial diameter Working time The time after which the initial cone would not flow at all under vibration is called working time. Flow decay Flow values measured as a function of time and displayed as a curve show with which speed an initial flow decays or can be maintained. Cold Crushing Strengths CCS were measured on 4x4x16 cm prisms dried or fired to 40C, 800C and 1100C respectively.

% passing

10

1 0,1 1 10 100 1000 10000 100000 particle size (microns)

Figure 3. Andreasen diagrams comparing particle size distributions between System 2 and 3.

Table II. Origin of raw materials used Tabular Alumina Spinel Reactive alumina MgO Silica fume Cement Additives T60 AR78 CT3000SG and P152B, CL370 Nedmag 99 (marine mgnesia) <0,2 mm and <0,4 mm 971U and OX50 Secar 71 and Secar 80 Dispersants : TPP, HMP, Darvan 7S, Castament FS10 Retarders : Boric acid, citric acid Accelerators : Lithium carbonate, sodium carbonate

Results

Influence of additives In Table III the working times for different systems and different admixtures are compared.
Table III. Working Times in System 2 and 4 for various admixtures (all values in min) TPP Spinel preformed Spinel forming 20 60 HMP 18 60 D7S+AC+NC 45 75

Testing

Flow value The flow value has been determined using a cone with 100 mm base diameter, 50 mm high and 70 mm top diameter. The cone is placed on a vibrating or shock table (ASTM 230C), filled with the castable, then taken away and after 25 blows (shock table) or 20 seconds of vibration the diameter of the resulting "cake" is measured and considered as the flow value in mm.

We see a clear difference between the two systems, the spinel system being clearly the more difficult to master in terms of working time. Results on flow decay for spinel forming systems have been presented elsewhere.5,6 Figure 4 shows the influence of Darvan 7S and HMP with or without additional retarder dosage on flow decay curves for a spinel castable. As a comparison the flow decay is also shown for a System 1 type formulation.

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Flow (mm) 250 200 150 100 50 0 0 15 30 45 Time (min) 60 D7S 0,05 + AB 0,02 HMP 0,05 + AB 0,01 HMP only Secar 80

and little decay during the first 60 minutes. The combination with retarders allows a reduction in the dosage rate. An accelerator is always necessary to control set. For triple admixtures, good results were found with sodiumcarbonate (NaC) and citric acid (AC). For the pure Castament FS10, Li2CO3 allows good results through the control of the flow decay. Working times measured on the vibrating table were virtually the same with 75 min for the two formulations containing accelerators. The effect of reducing the water demand is shown in Figure 6 for the different admixture systems.
Flow (mm) 260 240 220 200 180 160 3,5

Figure 4. Flow Decay for different additive combinations in spinel castables (preformed type).

We can come to three major observations : - A monoadditive formulation for HMP, TPP or Darvan 7S is not sufficient to give good flow behavior in preformed spinel castables. - These additives have to be combined with retarders to fully use their potential. This holds true for almost all formulation as already shown in earlier papers.7,8 - A CAC with 80% alumina can not necessarily always give a better performance because additive combinations allow more flexibility and enhanced performance with a 70% type cement. Figure 5 demonstrates the action of a high-range water reducing agent - such as Castament FS10.
Flow (mm) 250 200 150 100 50 0 0 30 Time (min) 15 45

4,5 5 Water addition %

5,5

D7S 0,05 + AC 0,02 + NC 0,008 D7S 0,05 + AB 0,022 + NC 0,001 D7S 0,05 + AB 0,02 HMP 0,06 + AB 0,01 Castament 0,08 Castament 0,08 + AC 0,012 + NC 0,005 AB HMP AC NC = = = = Boric acid Sodium hexa meta phosphate Citric acid Sodium carbonate

60

Castament 0,08 + AC + NC Castament 0,1 Castament 0,3 + Li2CO3

Figure 6. Vibration flow as a function of water addition for different admixture systems.

Figure 5. Flow decay for System 2 with different additives.

With combinations of admixtures or high-range water reducing agents, the casting water can be reduced drastically whilst still conserving a minimum flow necessary for placing by vibration. Strength development from green strength to CCS after 1100C heating is shown for the different admixtures in Figure 7.

This type of admixture when used alone displays very long working times, high initial flow values

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Influence of fine fillers

Cold Crushing Strength (MPa) 150 100 50 0

Alumina in the case of preformed spinel Figure 8 shows the influence of the reactive alumina on flow properties in the preformed spinel castable with additive package n1 as depicted in Figure 7.
Flow value (mm) 250 200 150 100 50 0 0 15 30 System 2 - A13 System 2 - A12 System 2 - A11 System 1

Additive 1

Additive 2

Additive 3

Additive 4

Additive 1 : Additive 2 : Additive 3 : Additive 4 : Additive 5 : Figure 7. System 2.

0,06 HMP + 0,01 BA 0,05 Darvan + 0,001 NC + 0,022 BA 0,3 Castament + 0,002 Li2CO3 0,05 Darvan + 0,008 NC + 0,02 CA 0,05 Castament + 0,005 NC + 0,012 CA CCS after hydration and heating for the spinel

Additive 5

1100C 800C 110C 24 hrs

45

60

Figure 8. Flow values for different aluminas in System 2 as compared to System 1. Table IV. Characteristics of the reactive aluminas used Al 1 BET Primary crystal size D50 Alumina Na2O m2/g micron micron % % 2,6 - 3,1 0,5 - 3,0 2,0 - 2,5 >99,8 0,06 Al 2 7,0 0,6 >99,7 0,08 Al 3 3,3 0,5 - 3,0 1,5 >99,8 0,03

The good flow and long working time could lead to lower green strength measured at 24 hours if no additional accelerator is used (compare additive 2,3 to 4,5). During heat up this effect will be overcome and decent CCS values after heating to 1100C can be achieved.

Figure 8 shows that the choice of the fine filler, in this case the alumina influences largely, working time, flow decay and flow level. The results shown are for a specific admixture combination but similar effects have been observed for other formulations. The fact that alumina 2 does not show any flow at all is partly due to the fact that the constant water addition used yielded a mix to dry to flow on the shock table. Placing by vibration was possible, however. These differences in flow behaviour attributable to the alumina type cannot be discerned or predicted by a study of the published characteristics on those aluminas.

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Silica fume in the case of spinel forming Formulations using the spinelforming logic mostly contain small amounts of silica fume as a fine reactive filler improving particle size distribution and hence flow. Upon heat up silica fume can also play a role as anti-slaking agent. The influence of different silica fume grades is shown in Figure 9.
Flow value (mm) 300 250 200 150 100 50 0 0 15 HMP + OX50 HMP + 971U TPP + OX50 TPP + 971U

an accelerator, which will lead to a three component admixture. The use of a high range water reducing agent does not necessarily need the addition of a retarder. For castables which contain preformed spinel the choice of reactive alumina is crucial. For castables of the spinel forming type, the choice of the silica fume influences largely workability.

Acknowledgements

The authors express their thanks and gratitude to all co-workers of Kerneos or Lafarge Central Research Laboratory for their support either in conducting the experimental work or their valuable discussion.

30

45

60

Figure 9. Flow decay in System 4 with monoadmixture and two different amorphous silica sources.

References

The replacement of 971U by OX50 gives longer working times, but slightly lower flow values especially during the first 30 minutes. This effect seems to come from physical (high specific surface area) properties but also from chemical interactions. These effects are investigated and discussed more detailed in 9.

1Naaby H.; Abildgaard O., Stallmann G., Whrmeyer, C. und Meidell, J. ; "Refractory wear mechanisms and influence on metallurgy and steel quality as a result of the conversion to endless lining at Det Danske Stalvalsevaerk" ; XXXVII Refractory Colloquium, October 1994, Aachen, GERMANY. 2Kanatani, T.; Imaiida, Y. ; "Application of an alumina-spinel castable to the teeming ladle for stainless steelmaking" ; UNITECR 1993. 3M. Rigaud, S. Palco, Ning Wang ; "Spinel formation in the MgO-Al2O3 system relevant to basic castables." ; UNITECR 1995. 4Zenbe-e Nakagawa, Naoya Enomoto, In-Suk Yi, and Keisuke Asano ; "Effect of Corundum/periclase sizes on expansion behavior during synthesis of spinel." ; UNITECR 1995.

Conclusions

The results presented show, as earlier observed for LCC or SFC castables, that the design and control of flow behavior, set and subsequent strength acquisition depend on the interaction of cement, filler and admixtures. In particular the following detailed conclusions can be expressed. - Dispersion agents work usually more efficient when combined with retarders what flow value and working time is concerned. - The additional design of setting time and strength development needs the inclusion of

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5Th. A. Bier et al, "Workability of calcium aluminates cement based castables containing magnesia" ; ALAFAR 1996 6Th. A. Bier, Ch. Parr, C. Revais, H. Fryda ; "Chemical interactions in calcium aluminate cement based castables containing magnesia.", to be published ; UNITECR 1997. 7Th. A. Bier, Ch. Parr ; "Admixtures with calcium aluminate cements and CAC based castables" presented at the 28th Annual SA Ceramic Society Symposium at Johannesburg, RSA 1996. 8Th. A. Bier, A. Mathieu, B. Espinosa and C. Marcelon ; "Admixtures and their interactions with high range calcium aluminate cement." ; UNITECR 1995. 9H. Fryda at al ; "Relation between setting properties of Low Cement Castables and Interactions within the binder system (CACFillers-Admixtures-Water)" ; UNITECR 1997.

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